Chemical process and product



Patented Nov. 6, 1945 CHEMICAL PROCESS AND PRODUUE Alger L. Ward,Bala-Cynwyd, Pa.,' assignor to The United Gas Improvement Company, acorporation of Pennsylvania No Drawing. Application June d, 1943, SerialNo. 489,693

7 Claims.

This application is a continuation-in-part of my copending applicationSerial Number 264,591, filed March 23, 1939.

The present invention relates to the production of aryl substitutedphenols.- More particularly, it relates to the production of arylsubstituted phenols by reacting phenols with unsaturated aromatichydrocarbons including unsaturated aromatic hydrocarbons boiling in therange of from 150 to 167 C. and obtained from light oil from thepyrolysis of petroleum oil.

The lower boiling condensate and the distillate from the tar produced inthe manufacture of carburetted water gas, oil gas, and the like, whichinvolve the pyrolysis of petroleum, is termed light oil. The higherboiling portion of the light oil contains a variety of unsaturatedaromatichydrocarbons mixed with saturated aromatic hydrocarbons ofneighboring boiling points.

For instance, the higher boilingportion of a light oil produced in'themanufacture of oil gas may contain styrene, ortho, para, and meta methylstyrene, indene, and other unsaturated aromatic hydrocarbons inadmixture with the xylenes, cumene, pseudo-cumene, durene, and possiblyother saturated aromatic hydrocarbons. These unsaturated hydrocarbonsmay be concentrated by further fractionation of the higher boilingportion of the light oil. For instance, alight oil produced in themanufacture of oil gas has been fractionated as follows to concentratethe following unsaturated aromatic hydrocarbons:

' Cut points, *0. styrene forerunnings 135 to 140 Styrene 140 to 15-0Unsaturates A1 150 to 160 Unsaturates A: 160 to 167 Methyl styrene group1 167 to 172 Methyl styrene group 2 1'72 to 175 ,Indene group 175 to 183Unsaturates 3B1 183 to 190 Unsaturates B: 190 to 200 The letters A1, A1,B1, and B2 refer to unsaturated aromatic unsaturated hydrocarbons andincluding unsaturated aromatic hydrocarbons boiling in the range from150 to 167 C., may be reacted with phenols to give mixed arylsubstituted phenols corresponding to the various aromatic unsaturatescontained therein, or preferably the ing in the range from 150 to 167 C.The con:

rately reacted with a phenol.

centration may be such as to yield a fraction having its 10% and boilingpoints within the recited range or the concentration may be such as toyield a fraction boiling substantially completely within the recitedrange.

The unsaturation contained in the light oil and boiling within the rangefrom to 167 C. may be subdivided, if desired, and the divisions sepamaybe advantageous to react with a phenol a light oil fraction having thepreponderant part of its unsaturation in the form of unsaturatedaromatic hydrocarbon material boiling in the range from 150 to C. Theconcentration may be such, that the 10% and 90% boiling points of thefraction fall between 150 and 160 C.. or substantially the entirefraction may boil between 150 and 160 C. Likewise a phenol may bereacted with a light oil fraction having the preponderant portion of itsunsaturation in the form of unsaturated aromatic hydrocarbon materialboiling in the range from 160 to 167 0., or having its 10% and 90%boiling points within that range, or boiling substantially completelywithin that range.

It may be desirable in the case of highly concentrated individualunsaturates or groups, to add an inert solvent such as a saturatedhydrocarbon prior to reaction with the phenol.

By phenols, I intend to mean the monoand polyhydroxy derivatives ofbenzene and its homologues, such as for instance, phenol, cresol,resorcinol, pyrogallol, hydroquinone, pyrocatechol, naphthols, and thelike, and substitution products of such compounds. As examples of acidssuitable as catalysts for the reaction, sulphuric acid and phosphoricacidmay be mentioned,

For example, it

I have found that the aryl substituted phenols produced in theperformance of my invention may be reacted with aldehydes to form resinswhich are soluble in drying oils, such as linseed oil and tung oil. Thischaracteristic gives them great value for use in varnishes and lacquersin which the usual phenol aldehyde condensation products cannot be useddue to their incompatibility with linseed oil and tung oil.

By aldehydes, it is intended to mean the aldehydes customarily employedin the production of phenol aldehyde condensation products of which, forexample, formaldehyde and furfural may be preferred because of theirrelative cheapnesa.

I have found that in the performance of my invention, in addition toproducing valuable aryl unsaturated aromatic hydrocarbons contained in.

such light oil fractions, the proportion of the mono substituted arylphenols with respect to diand tri-substituted phenols may be controlled,increasing excesses of phenol giving higher pro- 7 portions of monosubstituted products.

The invention will be further understood by reference to the followingillustrative examples:

Exsuru 1 Twelve mols of phenol (1128 grams) were weighed into a 3 neckedflask equipped with a stirring device, a'dropping funnel and athermometer. To this was added 1.2 cc. of 96% H2804. To this were added1684 grams of a light oil hydrocarbon fraction obtained during afractional distillation of light oil produced in the manufacture of oilgas by taking a cut over the temperature range 150-160. C. Thishydrocarbon fraction contained 28.0% of unsaturated materials by bromineanalysis (the unsaturatedmaterial being arbitrarily calculated asmonooleiine and having an average molecular weight of 118) and theweight used contained 4 mols of reactive hydrocarbon material. Thisaddition was performed dropwise with vigorous agitation. To facilitateagitation at the start of the reaction, the phenol was melted by heatingit on a water bath to about 42 C.

By variation of the rate of addition of the hydrocarbon fraction, thetemperature was maintained at approximately 45 C. during the entire timethe hydrocarbon was being added to the phenol catalyst mixture. The timerequired for this addition ofhydrocarbon material was 3-4 hours.

When addition of the hydrocarbon fraction had 2 hours.

ing about 2263 grams of unreacted phenol and saturated hydrocarbons, afraction was taken distilling over in the range 140-200 C. at 2-5 mm.absolute pressure, which weighed 494 grams (58.7%) of theory. Thisfraction was a viscous. oily liquid, phenolic in nature as shown bysubsequent tests. A solid residue remained in the distillation flask,amounting to 95.5 grams.

Color (Gardner Holt) 64 Sp. gr. D 20/4 1.0798 N 20/D 1.5860 Mol.weight"; 178.6 Zerewitinofl value"... per cent 90.8

This phenolic material evidently comprises a mixture 01' arylsubstituted phenols produced by reaction of the phenol with the aromaticunsaturates contained in this light oil cut.

Exam 2 6.6 mols of phenol (620, grams) were weighed into a 8 neckedflask equipped with a stirring device, a dropping tunnel and athermometer. To this was added 0.66 cc. H2804. To this were then addeddropwise 880 grams of a light oil hydrocarbon fraction obtained during afractional distillation of light oil produced in the manufacture of oilgas by taking a cut over the temperature range 160-167 C. Thishydrocarbon fraction contained 29.8% by weight of unsaturated materialsaccording to bromine analysis (the unsaturated material beingarbitrarily calculated as monoolefine and having an average molecularweight of 118) and the weight used therefor contained about 2.2 mols ofreactive hydrocarbon material. To facilitate agitation at the start ofthe reaction, the phenolwas melted by heating it on a water bath toabout 42 C.

By variation of the rate of addition of the hydrocarbon fraction, thetemperature was maintained at approximately 45 C. during the entire timethe hydrocarbon was being added to the phenol-catalyst mixture. The timerequired for this addition of hydrocarbon material was about 3 hours.

When addition of the hydrocarbon fraction had been completed heat wasapplied. The material was kept at a. temperature of l30-l60 C. for 2After cooling to C., the H2504 in the mixture was neutralized by addingthe calculated quantity of NarCOa dissolved in a few cc. of water.

The purification oi the desired condensation product and the recovery ofthe excess phenol and saturated hydrocarbon was accomplished as followsWithout washing or other treatment the reaction mixture was distilled.After collecting about 979 grams of unreacted phenol and saturatedhydrocarbons, a fraction was taken distilling ,over in the range -l96 C.at 2-3 mm. absolute pressure, which weighed 360 grams (about 77%theory). This fraction was a viscous, oily liquid, light amber in colorand phenolic in nature as shown by subsequent tests. A solid residueremained in the distillation flask amounting to 84 grams. This solidresidue need not be addition.

considered a waste as it has interesting properties indicative ofindustrial value.

The hydrocarbon and the unused phenol can each be recovered in arelatively pure state by simply conducting the distillation under afractionating column.

The material distilling in the range l40-196 C. at 23 mm. absolute,pressure, had the following physical properties:

Color (Gardner Holt) 5 Sp. gr. D 20/4, 1.0901 N 20/ 1.5915 M01. w i194.5 Zerewitinoif value percent 86.5

The phenolic material evidently comprises a mixture of aryl substitutedphenols, produced by reaction of the phenol with the aromaticunsaturates contained in the light oil out.

' Referring to Examples 1 and 2, the following table gives properties ofthe distillation residues produced therein.

Distillation of these residues gives very viscous semi-solid liquids ofdeep amber color constituting di-substituted phenols.

As before stated, the proportion of mono-substituted phenols totil-substituted and tri-substituted phenols produced in the reaction'maybe 40 controlled by controlling the proportion of phenol to theunsaturated aromatic hydrocarbons, a

molar excess of phenol having been found desirable when the desiredproducts are mono substituted phenols. However, the excess of phenol maybe limited by practical considerations and it may be desirable to employproportions resulting in the production of considerable proportions ofboth mono and di-substituted products.

For example, a molar ratio of phenol to fractlon unsaturation(considered arbitrarily for purposes of calculation as monoolefinicmaterial of Exlmru: 3 To two mols of phenol containing 0.2% by weight ofH2804 are added slowly a quantity of a cut takenfrom 150 to 160 C. of alight oil obtained, in the manufacture of oil gas. said quantitycontaining 1 mol. of unsaturation (arbitrarily calculated asmonooleflnic and having a molecular weight of 118). The temperature iskept below50p C. by regulation of the rate of When the light oil out isall added the mass is heated to 120-150 C. for 2 hours with agitation.After neutralization of the H2804 with the calculated amount of NazCOzsolution, the product is fractionally distilled. The fraction distillingabove 200 C. at 2-5 mm. will be found to be. principally thedisubstituted product;

Exsmru: 4

Following the same procedure as in Example 3, but employing a light oilout taken from 160 to 167 C. in sufllcient quantity to provide 1 mol ofunsaturation (arbitrarily calculated as mono- 'oleflnic and having anaverage molecular weight of 118), the distillation of the product willyield a fraction boiling above 196 C. at 2-5 mm. and containingprincipally the disubstituted product.

Itwill be seen from the examples given above, that the process of theinvention provides a simple and inexpensive separation of the productsof the reaction.

After, neutralization of the small quantity of acid, it is onlynecessary' to distill the products to recover separately the unreactedhydrocarbons,

and water, the unreacted phenol, and to separate the mono aryl phenolfrom di-aryl phenols and any higher substitution products, which areless valuable products. It is not necessary to wash out the acidcatalyst prior to distillation because of the small quantity employed.

The procedure permits the recovery of the saturated aromatichydrocarbons of the light oil fractions boiling in the range from 150 to167 C. and obtained in the pyrolysis of petroleum, which containconsiderable concentrations of aromatic unsaturates without the largewash losses incident to washing out the aromatic unsaturates and furtherprovides for recovering the aromatic unsaturates as valuable arylphenols.

For example, in the production of substituted phenols from the light oilunsaturation in the boiling range of from 150 to 167 C., recoveries ofsaturated aromatic hydrocarbons containing little olefinic contaminationare possible by frac: tional distillation of the product. The yield ofsaturated hydrocarbons may be as high as 75% or more of the light oilfraction employed.

As stated before, the aryl phenol produced in accordance with thepresent invention may be reacted with aldehydes to produce substitutedphenol-aldehyde resins which are compatible with drying oils, such aslinseed oil and tung oil.

EXAMPLE 5 Approximately 318 grams of the mono-substituted product ofExample 1 (corresponding to 1% mols of the mono-substituted phenol onthe basis of the assumed average molecular weight of 118 forthe'o'riginal unsaturates) are used in a specific preparation of avarnish resin. A wide boiling cut made from about 140 to 200 C. atapproximately 2-5 mm. pressure is used. The above quantity is reactedwith three mols grams) of formaldehyde in the form of an approximately37% solution and three grams of oxalic acid with agitation on a steambath for 24 hours. The reaction is carried out in a flask provided witha refluxcondenser. In order to compensate for the loss of formaldehydeby vaporization during the long heating period, the formaldehydesolution is added stepwise: 50% being added initially, 25% after 8 hoursand 25% after 16 hours. After the heating period, the reflux condenseris changed to a take-oil condenser, the temperature is raised to about200 (2., the system is evacuated to about 50 mm. pressure and the resinissteamed for two hours. The flask is cooled somewhat and the resin ispoured out while still molten.

The hardened resin is crushed and sieved. It will be found compatiblewith linseed and tung oil and may be cooked with these oils tofiormvarnishes. 1

The compatibility of these resins with the usually employed drying oils,linseed oil and tuna oil, is an extremely valuable characteristic. Itopens the door to the employment 01' phenol aldehyde condensationproducts in coating compositions, such as drying oil varnishes, andaflords a new utilization oi the unsaturated aromatic hydrocarbonscontained in light oil from petroleum pyrolysis, of which there i anextremely large potential supply.

The process herein described also 'aifords a more economical method ofrecovering the saturated aromatic hydrocarbons accompanyinl theunsaturated aromatic hydrocarbons in such light oil.

It is to be understood that the above particular description is by wayof illustration and that changes, omissions, additions, substitutions.and/or modifications may be made withinv the scope of the claims withoutdeparting from the spirit of the invention which is intended to belimited only as required by the prior art.

. I claim:

1. A proces comprising reacting a phenol with a light oil tractioncontaining unsaturated hydrocarbon material boiling within the rangefrom 150 to 167 C., said reaction taking placein the presence of acondensation catalyst, and said light oil having been obtained fromproducts of pyrolysis of petroleum oil.

2. A process comprising condensing a phenol in the presence of a mineralacid catalyst with a light oil fraction containing unsaturated aro--matic hydrocarbon material which boils in the range from 150 to 167 C.,said light oil having been obtained from products of pyrolysis producedinthe. manufacture of combustible gas by a process involving the thermaldecomposition of petroleum oil.

3.A process for producing aryl substituted phenol material comprisingreacting a phenol in the presence of a mineral acid catalyst with alight oil traction boiling preponderantly in the range from 150 to 167'C. and containing unsaturated aromatic hydrocarbon material boilingwithin said range, said light oil having been separated from Products ofpyrolysis obtained in comlight oil traction having 10% and boiling 1points within the range from to 167' C. and

containing aromatic unsaturation boiling within said range, said lightoil having been recovered from petroleum pyrolysis products.

5. A process for producing aryl phenol material comprising condensing aphenol in the presence of a mineral acid catalyst with a light oilfraction boiling preponderantly within the range from 150" to C. andcontaining aromatic unsaturation boiling in said range, said light oilhaving been obtained from products of petroleum oil pyrolysis.

6. A process for producing aryl phenol material comprising condensing aphenol with a light oil traction the preponderant part of which boils inthe range 160 to 187 C. and which contains aromatic unsaturation whichboils within said range, said light oil having been obtained fromproducts of pyrolysis of petroleum oil.

7. A process tor producing and phenol material comprising condensingphenol in the presence of sulfuric acid as a cataLyst with a fraction oia light oil obtained from petroleum oil pymlisis products, said fractioncontaining unsaturated aromatic hydrocarbon material which boils with-40 in the range from 150 to 167- C., said condensa-

